JPS6284168A - Polishing-type antifouling paint composition - Google Patents

Abstract

PURPOSE:To provide the titled composition for ship, etc., containing a specific metal-containing resin composition as a vehicle, slowly releasing an antifouling agent to eliminate the surface-roughness of a coating film and keeping antifouling effect for a long period. CONSTITUTION:The objective composition contains, as a vehicle, a metal- containing resin composition composed of a resin having at least one group of formula I [X is group of formula II, III, IV or V; M is metallic atom having a valence of >=2 (e.g. metals of groups IIa, IIb, IIIa, etc., of the periodic table excluding Zn, Cu and Te); X is 1-2; m is >=1; n is 0 or >=1 (m+n+1 is valence of metal M); R1 is 1-10C hydrocarbon group; R2 is an organic compound residue having antifouling activity and bonded to the metal atom M via the bond of formula VI, VII, VIII, -S-, IX, X or XI] at the terminal of at least one side chain.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a polishing type antifouling paint composition containing a novel metal-containing resin composition as a vehicle.

Conventional technology Today, it is widely practiced to form organic or inorganic antifouling agents into paints with binders such as vinyl resins and alkyd resins and paint them as ship bottom paints. Since the elution rate of the antifouling agent is mainly based on the diffusion phenomenon caused by its concentration gradient, a stable antifouling effect cannot be expected for a long time, and the antifouling agent is After being eluted from the water, the water-insoluble resin components form a skeleton structure, which causes many problems such as increased frictional resistance between the ship and the water, reduced speed, and increased fuel consumption. Therefore, antifouling paints made of antifouling agents and hydrolyzable resin vehicles that create relatively strong coatings and gradually hydrolyze in seawater to dissolve the resin have been attracting attention. It's arrived.

The present inventors previously discovered that a hydrolyzable polyester resin in which a large number of metal-ester bonds are incorporated into the polyester main chain is extremely useful as a vehicle for polishing-type antifouling paints. No. 5
A patent application was filed as No. 8-196900. In such resins, the metal-ester moiety is easily hydrolyzed under alkaline conditions such as seawater, and the resin is dissolved into segments with small molecular weights, but the resin itself originally has a relatively small molecular weight. (for example, up to about 2,000), which causes problems such as poor film-forming properties and a tendency to cause cracks and peeling of the coating film.

Increasing the molecular weight of the polyester resin certainly improves film-forming properties, but the hydrolyzability becomes extremely poor, and to compensate for this drawback, increasing the metal-ester concentration in the polyester main chain makes it easier to use polar solvents. This creates a new problem of solvent insolubility, which can only be dissolved in seawater, causing the coating film to swell in seawater.
Undesirable.

As a hydrolyzable resin, for example, it has been attempted to have a trialkyl tin ester at the end of the side chain, and to gradually increase the polarity of the resin by hydrolyzing the ester moiety to achieve dissolution and elution. A typical example thereof is an acrylic resin containing triorganotin salts of α, β-, and β-basic acids as constituent units. In this case, in order to create a stable and strong coating film, the resin should preferably be a polymer that does not contain hydrophilic groups as much as possible, and in order for the decomposed resin to be dissolved in water, It must be ensured that the resin has a hydrophilic group concentration above a certain critical value. Therefore, it is common practice to copolymerize triorganotin salts of α, β-, and β-basic acids with acrylic vinyl monomers, so that the former is present in a high concentration, and the parent wood group is removed as much as possible from the latter. , e.g. 55-70wt%
Copolymers of α,β-unsaturated acid-base acid triorganotin salts with acrylic acid esters, acrylamide, styrene, etc. have been put into practical use. Unlike polyester-type resins containing metal ester bonds in the main chain, these resins generate hydrophilic carboxyl groups when the triorganotin moieties in the side chains are released by hydrolysis, and their concentration reaches a certain critical value. However, it is necessary to use large amounts of expensive organic tin compounds, and from a public health standpoint, it is important to reduce or stop their use as much as possible. Avoidance is desired.

Therefore, it is a resin with excellent film-forming properties that has a group on the side chain that can generate parent wood groups by hydrolysis, and is eluted with moderate hydrolysis in seawater, and is expensive. It is clear that if a new hydrolyzable resin composition that does not rely on triorganotin salts, whose use is considered undesirable from a public health standpoint, could be obtained, it would be extremely useful as an antifouling paint. be. The present inventors have proposed, as a means to solve this problem, that the terminal end of at least one side chain OOH or -P; M is a zinc, copper or tellurium atom; X is an integer of 1 to 2; -O- A metal-containing resin composition comprising a resin having at least one group represented by C-R-8-R1 or ■ and a metal-containing resin composition in which M is a zinc, copper or tellurium atom as a vehicle. Discovered a coating composition characterized by
No., filed on May 17, 1985).

In the invention related to the above application, when a metal-containing resin undergoes hydrolysis in seawater (weakly alkaline), hydrophilic groups of carboxylic acid, sulfonic acid, or phosphoric acid are generated in the side chain portion, and the concentration reaches a certain critical value. Then, the resin itself is eluted into the seawater, and the metal part is also cut off between O and M and between M and R in 10-M-R due to hydrolysis, and the metal parts are made of zinc, copper or tellurium, which have antifouling properties. This was based on the discovery that it is extremely useful as a resin vehicle for antifouling paints because it generates metal ions. However, relying only on such metal ions for antifouling performance is unrealistic due to the relationship between the metal content in the resin and the rate of hydrolysis. Rather, it is necessary to add a regular antifouling agent separately, and to determine the degree of depletion of the resin and the antifouling performance. Balancing performance is considered an easy and practical solution.

Problems to be Solved by the Invention Therefore, the main object of the present invention is to have a resin in its side chain that has a group capable of producing a parent wood group by hydrolysis, and which can undergo moderate hydrolysis and be eluted in seawater. It is a resin with excellent film-forming properties for molds, and when hydrolyzed, a compound with excellent antifouling performance is liberated and exhibits an effective antifouling effect. It is an object of the present invention to provide an antifouling paint containing a new type of hydrolyzable resin composition as a resin vehicle, which can be arbitrarily selected from a wide variety of types and serves only to bind staining compounds.

Means for solving the problem - P-bond; M4 is a metal atom with a valence of 2 or more (excluding zinc, copper, and tellurium); x is an integer of 1 to 2; m is an integer of 1 or more; n
is an integer of 0 or 1 or more (however, m+n+1 is equal to the valence of the metal M); R4 is a hydrocarbon having 1 to 10 carbon atoms; This can be achieved by providing an antifouling paint composition characterized by containing as a vehicle a metal-containing resin composition comprising a resin having at least one group represented by the following formula.

In the coating composition of the present invention, the metal-containing resin composition used as the resin vehicle is characterized by having at least one group represented by the above formula at the end of the side chain,
For example, it can be easily manufactured by any of the following methods.

That is, a method in which a polymerizable unsaturated monomer having a metal ester moiety of an organic acid having antifouling properties at the end is synthesized in advance and copolymerized with another polymerizable unsaturated monomer; A resin obtained by copolymerizing an organic acid monomer with other polymerizable unsaturated monomers is reacted with a metal oxide, chloride, or hydroxide and a monovalent organic acid having antifouling properties. Alternatively, there is a method of transesterification using a metal ester of the -valent organic acid. More specifically, the resin composition of the present invention is produced as follows.

(1) (a) Metal oxide, hydroxide, sulfide, or chloride; (b) monovalent organic acid or alkali metal salt thereof having antifouling properties; and (c) polymerizable unsaturated organic heating an acid or its alkali metal salt below the decomposition temperature of the metal salt;
Stir and optionally add by-product alkali metal chloride, water,
A metal ester of a -valent organic acid and a metal ester of a difunctional polymerizable unsaturated organic acid are separated to obtain a purified polymerizable unsaturated organic acid and a metal ester of a monovalent organic acid having antifouling properties.

In the above reaction, the amounts of (,), (b), and (Q) do not necessarily have to be equal equivalents;
The desired product can also be obtained using 8 to 3 equivalents and 0.8 to 2 equivalents of (c).

The thus obtained metal esterified product of a polymerizable unsaturated organic acid and a monovalent organic acid having antifouling properties or a mixture of the metal ester and a monovalent organic acid metal ester can be homopolymerized or copolymerized with other methods. Copolymerization with monomers leads to the desired resin having a metal ester moiety at the end of the side chain. or (2) (d) a resin containing an organic acid or an alkali metal salt thereof in its side chain; (e) a metal oxide, hydroxide, sulfide, or chloride; and (f) a resin having antifouling properties. heating and stirring a divalent organic acid at a temperature below the decomposition temperature of the metal salt,
If desired, by-products can be separated and purified to obtain a resin having a metal ester moiety in the resin side chain. The ratio of raw materials used in this reaction is 0.8 to 1.5 equivalents (particularly preferably 1 equivalent) to 1 equivalent of organic acid in resin (d).
．． 0 to 1.2 equivalents), and (f) is preferably 0.8 to 2 equivalents (particularly preferably 1.0 to 1.5 equivalents).

In addition, when selecting a monovalent organic acid with a low boiling point and using a reaction format that involves a dehydration reaction, the monovalent organic acid is distilled out of the system along with water, and metal ester bonds are formed between the resins, resulting in an increase in viscosity or gelation. (f) It is preferable to use the amount above the above because there is a risk of chemical reaction, or (3) a metal ester of a monovalent organic acid having antifouling properties is added to the resin (g) having an organic acid in the side chain. h) is reacted at a temperature below its decomposition temperature, and a metal ester moiety is introduced at the end of the resin side chain by transesterification.

In this reaction, if the monovalent organic acid has a low boiling point (for example, acetic acid), the acid may come out of the system upon heating and metal ester bonds may be formed between the resins, so the reaction must proceed carefully. The amount (h) is usually 0.3 to 3 equivalents per equivalent of the organic acid in the resin (g).

Preferably it is 0.4 to 2.5 equivalents. Examples of the polymerizable unsaturated organic acid (Q) used in the above method include methacrylic acid, acrylic acid, p-styrenesulfonic acid, 2-
Methyl-2-acrylamidopropanesulfonic acid, methacrylic acid phosphooxypropyl, methacrylic acid 3
-chloro-2-acidophosphooxypropyl, acidophosphooxyethyl methacrylate, itaconic acid, (anhydrous)
maleic acid, monoalkyl itaconate (e.g. methyl,
ethyl, butyl, 2-ethylhexyl, etc.), monoalkyl maleate (e.g. methyl, ethyl, butyl, 2-ethylhexyl, etc.); herfestation of OH group-containing polymerizable unsaturated monomers and acid anhydrides, such as (meth)acrylic acid 2-
Examples include hafesters of hydroxyethyl such as succinic anhydride, maleic anhydride, and phthalic anhydride, and one type or a combination of two or more of these can be used.

As the monovalent organic acid (b) having antifouling properties, any aliphatic, aromatic, alicyclic, or heterocyclic organic acid can be used as long as it has antifouling properties, and representative ones are as follows. It is.

(1) Those having -0-C- bonds, such as alicyclic carboxylic acids such as naphthenic acid; salicylic acid,
Cresotic acid, α-naphthoic acid, β-naphthoic acid, p-
Aromatic carboxylic acids such as oxybenzoic acid; halogen-containing aliphatic carboxylic acids such as monochloroacetic acid and monofluoroacetic acid; 2,4.5-trichlorophenoxyacetic acid, 2,4
- Halogen-containing aromatic carboxylic acids such as dichlorophenoxyacetic acid; organic nitrogen-containing carboxylic acids such as quinoline carboxylic acid, nitrobenzoic acid, dinitrobenzoic acid, and nitronaphthalene carboxylic acid; lactone carboxylic acids such as pulpic acid and purpic acid (2 ) -S-C- bond dithiocarbamates such as dimethyldithiocarbamate (3) -0-8- bond ■ 1-naphthol-4-sulfonic acid, paraphenylbenzenesulfonic acid, β-naphthalenesulfonic acid , sulfur-containing aromatic compounds such as quinoline sulfonic acid, triethylpyrophosphoric acid, dimethylamino phosphate, and other various organic phosphoric acid compounds (5) Compounds having an -8- bond (6) Compounds having an -0-C- bond These are typical examples of organic acids that can be used, but the present invention is not limited to such organic acids. It is kept immersed in seawater for a certain period of time.

Any organic acid can be used as long as it is a compound that has antifouling properties according to a simple test such as checking the adhesion state of marine organisms on gold wire.

In addition, the metal species used in the present invention include the na group of the periodic table excluding zinc, copper, and tellurium (e.g., Ba),
b group (e.g. Cd, Hg), Hg group (e.g. Al),
Metals such as group IVa (e.g. Sn, Pb, Si), group VIa (e.g. Se), group VIb (e.g. Cr, Mo), group IIb (e.g. Mn), group II (e.g. Fe, Co, Ni), etc. It will be done.

These metals are usually used in the form of oxides, hydroxides, and chlorides, but halides other than chlorides, nitrates, sulfates, carbonates, etc. can also be used if desired. Furthermore, organic metal salts such as dibutyltin oxide can also be used.

Since the resin composition used in the present invention has an organic acid residue having antifouling properties in the side chain, it is not necessarily necessary to use a metal having antifouling properties, but it has a metal having antifouling properties and a metal having antifouling properties. It is expected that the antifouling performance will be further improved by using an organic residue in combination. Other polymerizable unsaturated monomers used in copolymerization are not particularly limited and any copolymerizable monomers known to those skilled in the art may be used, such as (meth)acrylic acid. methyl,
Ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene, vinyltoluene, vinylpyridine, vinylpyrrolidone, vinyl acetate , acrylonitrile, methacrylonitrile, dimethyl itaconate, dibutyl itaconate, di-2-ethylhexyl itaconate, dimethyl maleate, di(2-ethylhexyl) maleate, ethylene, propylene, vinyl chloride, and the like.

Further, if desired, OH-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. can also be used.

Resin (d) having an organic acid in the side chain used in the present invention (
Examples of g) include not only vinyl resins but also resins containing organic acids such as polyester resins, oil-modified alkyd resins, fatty acid-modified alkyd resins, and epoxy resins.

In the resin having an antifouling-valent organic acid metal ester at the end of the side chain used in the present invention, it is not necessary that all the organic acids in the side chain of the resin have such a metal ester bond, and if desired, free organic acid groups may be It is okay to leave it as is to some extent.

The molecular weight of the resin of the present invention obtained by the above method is not particularly limited, but the number average molecular weight is 4000.
~40,000 is preferable, and 60 is particularly preferable.
The range is from 00 to 35,000. This is because, if it is less than 4,000, the film forming properties of the paint will be insufficient and cracks and peeling may occur.

On the other hand, if it exceeds 40,000, the storage stability of the paint deteriorates, making it unsuitable for practical use, and it also requires a large amount of diluting solvent during coating, which is unfavorable from the viewpoint of public health and economic efficiency.

The resin composition of the present invention can be used for coating underwater structures, and has the characteristic that the coating or film is gradually hydrolyzed and eluted in an alkaline atmosphere, and is useful, for example, as a coating for fishing nets, an antifouling coating for ships, etc. be.

As already mentioned, unlike polyester resins that have many metal ester moieties in the main chain, the resin of the present invention has metal ester bonds at the end of the side chain, and when hydrolyzed in an alkaline atmosphere, the resin becomes small. Rather than being broken down into segments and eluted all at once, parent wood groups are generated in the side chain portions, and their concentration reaches a certain critical value before being eluted. Therefore, when used as a vehicle for ship bottom paint, it has the characteristic of being able to control the antifouling period over a long period of time. The metal content required for the resin to dissolve into seawater is 0.3w in the resin.
The range of t% to 20wt% is preferable, especially 0.5wt%
It has also been found that ~15 wt% is optimal. This is because if the metal content in the resin is less than 0.3 wt%, elution from the resin will be extremely slow even if the metal ester moiety is hydrolyzed, and if it exceeds 20 wt%, the elution rate will be too fast, both of which are undesirable. It is.

The acid value and hydroxyl value in the metal-containing resin of the present invention are not necessarily O.
It is not necessary that the resin is dissolved or eluted in water, and it is acceptable to a certain extent. More specifically, the acid value is up to 40 KOH/g, preferably 30 KOH
/g, hydroxyl value up to 200KOH+ag/g, good:
! -L<4!Up to 150 KOH/g is an acceptable range.

In the antifouling paint of the present invention, the above resin composition is used as a resin vehicle, and this resin undergoes gradual hydrolysis in seawater (weakly alkaline), and the concentration of hydrophilic groups in the resin increases until it reaches a certain critical value. When reached, the resin is eluted, and the metal itself combines the resin with hydrophilic groups and the organic acid with antifouling properties.
It is used only for the purpose of separating the two by hydrolysis, and has the characteristic that when hydrolyzed, a monovalent organic acid with antifouling properties is released into seawater. It can be selected from a wide range depending on the hydrolysis rate, and the effective antifouling effect does not depend on the monovalent organic acid at the end of the side chain without adding any other antifouling agent.
It can be said to be an extremely new and useful resin.

When making a paint, any pigment, solvent, etc. are selected as appropriate, and an antifouling paint is made by a conventional method.

As already mentioned, since the resin composition of the present invention has antifouling properties itself, there is no need to add other antifouling agents, but if desired, other known antifouling agents may be added to the paint.

A disinfectant or the like may be added. Such agents include, for example, bis(tributyltin) oxide, tributyltin chloride, tributyltin fluoride, tributyltin acetate, tributyltin nicotinate, tributyltin persate, bis(tributyltin) alpha.
, α′-dibrom succinate, triphenyltin hydroxide, triphenyltin nicotinito, triphenyltin persate, bis(triphenyltin)
It is also possible to use it in combination with organic tin compounds such as α,α'-dibromsuccinate and bis(triphenyltin) oxide. In addition, commonly used coloring pigments, extender pigments, organic solvents, etc. can be freely selected and used.

The compositions of the invention can be prepared by methods known per se in the paint manufacturing art.

For compounding, known machines such as ball mills, Hebrew mills, roll mills, speed run mills, etc. can be used.

The antifouling paint made using the resin composition of the present invention exhibits a stable antifouling effect over a long period of time, and is comparable in performance to conventional antifouling paints based on triorganotin-containing acrylic resins. Moreover, since it does not rely on expensive triorganic tin, it has the advantage of significantly reducing costs and avoiding public health problems.

The present invention will be explained below with reference to Examples. Parts and percentages are by weight unless otherwise specified.

Varnish Production Example 1 120 parts of pheasant roll and 30 parts of n-butanol are added to a four-bottle flask equipped with a stirrer, a reflux condenser and a dropping funnel, and the temperature is maintained at 110°C to 120°C.

In this solution, 60 parts of ethyl acrylate, 2-acrylic acid,
A mixed solution of 25 parts of ethylhexyl, 15 parts of acrylic acid, and 2 parts of azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours, and the temperature was kept for 2 hours after the addition.

Varnish A was obtained with a resin solution having a solid content of 39.8% and a viscosity of 2.2 poise.

Varnish Production Example 2 Into the same reaction vessel as in Varnish Production Example 1, 75 parts of Kijirole and 75 parts of n-butanol were added and kept at 110°C. In this solution, 50 parts of n-butyl methacrylate, 45 parts of methyl methacrylate, 5 parts methacrylic acid, 2 parts benzoyl peroxide
A mixed solution of 1 part was added dropwise over 3 hours, and the mixture was kept warm for 2 hours. The solid content was 39.8% and the viscosity was 0.8 poise. In this, methanol of sodium hydroxide 5νt/ii
Varnish B was obtained by adding 46 g of t% solution.

Resin production example 1 To a reaction vessel similar to varnish production example 2, 100 parts of toluene, 172 parts of barium hydroxide, 86 parts of methacrylic acid, and 167 parts of nitrobenzoic acid were added and reacted at 120°C for 3 hours under air bubbles to produce a resin. water was removed. Next, insoluble matter was filtered off. This solid content was confirmed to contain vinyl groups and barium carboxylate by IR.

100 parts of this toluene solution was added to the same reaction solution as in Varnish Production Example 1, 150 parts of xylene was added, and the temperature was raised to 100°C. 150 parts of methyl methacrylate and 2 parts of azobisisobutyronitrile were added dropwise to the mixture over 3 hours, and the mixture was kept warm for 2 hours. Varnish V-1 was obtained with a solid content of 55.9% and a viscosity of 2.3 poise. The barium content of this varnish was determined by fluorescence X-ray method, and the barium content was 5.2w.
It was t%. The presence of nitrobenzoic acid was also confirmed by UV absorption.

Resin Production Example 2 100 parts of varnish A, 11.5 parts of salicylic acid, and 7.5 parts of iron hydroxide were added to a four-bottle flask equipped with a stirrer, a reflux condenser, and a decanter, and the temperature was raised to 120°C and kept for 2 hours. .

During this time, the water produced was removed. (Dehydrated amount: 2.8 g) The obtained varnish V-2 was green in color, had a solid content of 48.7%, and had a viscosity of 2.3 poise. This varnish was reprecipitated with white spirit, and the iron in the green resin obtained was determined in the same manner as in Resin Production Example 1.
It contained t%. The presence of salicylic acid in the resin was confirmed by UV absorption.

Resin Production Example 3 150 parts of varnish A, 17.3 parts of salicylic acid, and 30.2 parts of lead hydroxide were added to the same reaction vessel as in Resin Production Example 2.
The temperature was raised to 0°C and kept for 2 hours. During this time, the water produced was removed. (Dehydrated amount: 4.2 g) Solid content of the obtained varnish: 5
A varnish V-3 of 1.9% and a varnish viscosity of 2.5 poise was obtained. This varnish was reprecipitated from white spirit, and lead in the resulting resin was quantified in the same manner as in Resin Production Example 1.6.
It contained 8 wt%. The presence of salicylic acid in the resin was confirmed by UV absorption.

Resin Production Example 4 Into the same reaction vessel as in Resin Production Example 2, 100 parts of varnish A,
14.4 parts of 5-quinolinecarvone fi and 7.7 parts of nickel hydroxide were added, the temperature was raised to 120°C, and the temperature was kept for 2 hours.

During this time, the water produced was removed. (Dehydrated amount: 2.7 g) The obtained varnish was pale green, had a solid content of 50.4%, and had a varnish viscosity of 2.5 voids. Varnish V-4 was obtained. This varnish was reprecipitated from white spirit, and the nickel in the resulting light green resin was quantified in the same manner as in Resin Production Example 1.
．． It contained 5 wt%.

Resin production example 5 Varnish B was placed in a four-loaf flask equipped with a stirrer and a reflux condenser.
100 parts of sodium salicylate, 3.7 parts of sodium salicylate, and 6.2 parts of mercurous chloride were added thereto, reacted at 120°C for 2 hours, and filtered to obtain Varnish V-5.

This varnish had a solid content of 40.7% and a viscosity of 1.2 poise. The Hg content of this varnish was determined in the same manner as in Resin Production Example 1, and the Hg content was 3.6 wt%.

Resin Production Example 6 Into the same reaction vessel as in Resin Production Example 5, 150 parts of Varnish B,
4.0 parts of monochloroacetic acid Na salt and 4.5 parts of nickel chloride were added, and the mixture was reacted at 120°C for 2 hours and filtered to obtain varnish V-6. This varnish has a pale green color and has a solid content of 40
．． 2%, and the viscosity was 1°8 poise. The Ni content of this varnish was determined in the same manner as in Resin Production Example 1, and the Ni content was 1.
It was 0wt%.

Resin Production Example 7 Into the same reaction container as in Resin Production Example 5, 100 parts of varnish B,
6.5 parts of triethylpyrophosphate Na salt, 3 parts of nickel chloride
．． Add 0 parts, react at 120°C for 2 hours, filter,
Varnish V-7 was obtained. This varnish was pale green in color, had a solid content of 41.2%, and a viscosity of 2.3 poise. The Ni content of this varnish was determined in the same manner as in Resin Production Example 1, and the Ni content was 0.9 wt%.

Resin Production Example 8 Into the same reaction vessel as in Resin Production Example 2, 100 parts of varnish A,
18.1 parts of nitronaphthalene carboxylic acid and 6.5 parts of aluminum hydroxide were added, the temperature was raised to 120°C, and the temperature was kept for 2 hours. During this time, the water produced was removed. (Dehydrated amount: 2.6g
) Varnish V-8 was obtained with a solid content of 51.3% and a varnish viscosity of 1.9 poise. This varnish was reprecipitated from white spirit, and the amount of A1 in the resulting resin was determined in the same manner as in Resin Production Example 1, and the content was 1.8 wt%.

Resin Production Example 9 In a reaction vessel similar to Varnish Production Example 1, 100 parts of toluene, 89 parts of manganese hydroxide, 86 parts of methacrylic acid, 2,4
-221 parts of dichlorophenoxyacetic acid was added, and the mixture was reacted at 120° C. for 3 hours under air bubbles to remove generated water.

Next, insoluble matter was filtered off. Vinyl groups and Mn carboxylate were confirmed in this solid content by IR.

100 parts of this toluene solution was added to the same reaction solution as in Varnish Production Example 1, and 200 parts of xylene were added.

Raise the temperature to 100°C. In this, methyl methacrylate 15
0 parts of azobisisobutyronitrile and 2 parts of azobisisobutyronitrile were added dropwise over 3 hours, and the mixture was kept warm for 2 hours. The solid content of this varnish is 48.8%
A varnish V-9 having a viscosity of 1.8 poise was obtained. The Mn content of this varnish was determined in the same manner as in Resin Production Example 1, and the Mn content was 1.5 wt%.

Resin Production Example 10 Into the same container as in Resin Production Example 2, 100 parts of varnish A, 16.1 parts of benzenesulfonic acid chloride, and 14.3 parts of barium hydroxide were added, the temperature was raised to 120°C, and the temperature was kept for 2 hours. During this time, the water produced was removed. (Dehydrated amount: 2.5 g) Solid content of the obtained varnish: 52.3%, viscosity of the varnish: 2.4
Poise varnish v-10 was obtained. This varnish was reprecipitated from White Spirit 1-, and barium in the resulting resin was determined in the same manner as in Resin Production Example 1, and was found to contain 7.9 wt%.

Resin Production Example 11 To a reaction vessel similar to Varnish Production Example 1, 100 parts of toluene, 90 parts of iron hydroxide, 86 parts of methacrylic acid, and 152 parts of dimethylamino phosphate were added, and the mixture was heated at 120°C under air bubbles for 30 minutes.
The water produced by the reaction was removed. Next, insoluble matter was filtered off.

This solid content was confirmed to contain vinyl groups and iron carboxylate by IR.

100 parts of this toluene solution was added to the same reaction solution as in Varnish Production Example 1, 150 parts of xylene was added, and the temperature was raised to 100°C. 150 parts of methyl methacrylate and 2 parts of azobisisobutyronitrile were added dropwise to the mixture over 3 hours, and the mixture was kept warm for 2 hours. A varnish v-11 having a solid content of 52.2% and a viscosity of 2.8 poise was obtained.

The iron content of this varnish was determined in the same manner as in Resin Production Example 1,
The iron content was 2.9 wt%.

Resin Production Example 12 To a reaction vessel similar to Varnish Production Example 2, 100 parts of toluene, 249 parts of dibutyltin oxide, 86 parts of methacrylic acid, and 138 parts of salicylic acid were added, and the mixture was heated at 120°C under air bubbles.
The reaction was carried out for 3 hours and the produced water was removed. Next, insoluble matter was filtered off. The solid content of the obtained toluene solution was confirmed to contain vinyl groups and tin carboxylate by IR.

100 parts of this toluene solution was added to the same reaction solution as in Varnish Production Example 1, 200 parts of xylene were added, and the temperature was raised to 100°C. 150 parts of methyl methacrylate and 2 parts of azobisisobutyronitrile were added dropwise into the mixture over 3 hours, and the mixture was kept warm for 2 hours. Varnish V-12 was obtained with a solid content of 49.2% and a viscosity of 2.1 poise. The tin content of this varnish was determined in the same manner as in Resin Production Example 2, and the tin content was 4.2 wt%.

Resin Production Example 13 Into the same reaction vessel as in Resin Production Example 2, 100 parts of varnish A,
14 parts of nitrobenzoic acid, 20.7 parts of dibutyltin oxide
The mixture was heated to 120°C and kept for 2 hours. During this time, the water produced was removed.

(Dehydrated i1.2g) The obtained varnish has a solid content of 53.8%
, varnish v-13 having a viscosity of 2.3 poise was obtained.

This varnish was reprecipitated from white spirit, and the tin content in the resulting resin was determined by fluorescence X-ray method.

It contained 6.5 wt%.

Resin Production Example 14 Into the same reaction vessel as in Resin Production Example 2, 150 parts of varnish A,
11.8 parts of monochloroacetic acid, 31 parts of dibutyltin oxide
The mixture was heated to 120°C and kept for 2 hours. During this time, the water produced was removed.

(Dehydrated amount: 1.9 g) The resulting varnish has a solid content of 51.8%.
, varnish v-14 having a viscosity of 2.1 poise was obtained. This varnish was reprecipitated from white spirit, and the tin content in the resulting resin was determined by fluorescent X-ray method to be 6.8 wt%.

Resin production example 15 Varnish B was placed in a four-loaf flask equipped with a stirrer and a reflux condenser.
100 parts of sodium diethyldiocarbamate and 3.0 parts of nickel chloride were added thereto, and the mixture was reacted at 120°C for 2 hours, followed by filtration to obtain varnish v-15. This varnish had a solid content of 39.2% and a viscosity of 1.2 voids. The Ni content of this varnish was determined in the same manner as in Resin Production Example 2, and the Ni content was 0.9 wt%.

Resin Production Example 16 Into the same reaction vessel as in Resin Production Example 2, 100 parts of varnish A,
14.4 parts of 5-quinolinecarboxylic acid and 20.7 parts of dibutyltin oxide were added, the temperature was raised to 120°C, and the temperature was kept for 2 hours. During this time, the water produced was removed. The obtained varnish was 51.6%, and the viscosity of the varnish was 2.3 poise.
I got 16.

This varnish was reprecipitated from white spirit, and the Sn content in the resin was determined by fluorescent X-ray method and was found to be 5.1 wt%.

Comparative varnish production example 1 Varnish A of Varnish Production Example 1 is referred to as Comparative Varnish A.

Comparative Varnish Production Example 2 100 parts of varnish A, 16.7 parts of lauric acid, and 20.7 parts of dibutyltin oxide were added to a four-roof flask equipped with a stirrer, a reflux condenser, and a decanter, and the temperature was raised to 120°C. It was kept warm for hours. During this time, the water produced was removed. The resulting varnish was Comparative Varnish B having a solid content of 54.5% and a varnish viscosity of 1.9 poise. This varnish was reprecipitated from white spirit, and the tin content in the resulting resin was determined by fluorescent X-ray method to be 6.3 wt%.

Comparative Varnish Production Example 3 100 parts of pheasant roll was added to a four-bottle flask equipped with a stirrer, a reflux condenser, and a dropping funnel, and the temperature was maintained at 80°C to 85°C. A mixed solution of 50 parts of methyl methacrylate, 40 parts of 2-ethylhexyl methacrylate, and 1.5 parts of azobisisobutyronitrile was dropped into this solution at a uniform rate over 3 hours, and the mixture was kept warm for 2 hours after the dropwise addition. Next, 10 parts of nitrobenzoic acid,
8 parts of iron hydroxide was added and stirred at 120° C. for 2 hours to obtain comparative varnish C with a resin solution having a solid content of 50.2% and a viscosity of 3.9 poise.

This varnish was reprecipitated in the same manner as in Resin Production Example 2, and the iron content in the resin was quantified. The iron content was less than 0.01 wt%, and the resin did not contain nitrobenzoic acid based on UV absorption. It was confirmed.

Example 1 45 parts by weight of varnish V-1 obtained in Resin Production Example 1.

20 parts by weight of cuprous oxide, 20 parts by weight of zinc white, 2 parts by weight of colloidal silica, 5 parts by weight of titanium oxide, 5 parts by weight of red iron oxide, and 3 parts by weight of n-butanol were dispersed in a ball mill for 5 hours to form a coating composition. Obtained.

Examples 2 to 16 and Comparative Examples 1 to 3 Using the resin varnishes obtained in Resin Production Examples 2 to 16 and Comparative Varnish Production Examples 1 to 3, the respective coating compositions were prepared according to Example 1 according to the coating formulations shown in Table 1. I got something.

Table 1 (Continued) The varnishes used in Paint Consumption Test Examples 1 to 16 and Comparative Examples 1 to 3 were
(As a clear paint) applied to a test plate to a dry film thickness of approximately 140μ, this test plate was attached to a disc rotor plate, and sprayed in seawater (water temperature 20°C ± 2°C) at a constant speed (peripheral speed approximately 30 knots) for 4 months. The elution film thickness was measured by rotating day and night. The results are shown in Table 2.

(Margin below) pIl, membrane depletion test Table 2 Comparative Example 1 was completely eluted after 3 months.

Antifouling performance test Each paint obtained in Examples 1 to 16 and Comparative Examples 1 to 3 was applied twice to a sandblasted steel plate that had been previously coated with antirust paint so that the dry film thickness was approximately 200μ. A brush-coated test board was prepared, and an antifouling performance test was conducted using a test paper in Aioi Bay, Hyogo Prefecture, using a dipping test. The results are shown in Table 3, and the paints of Examples 1 to 16 showed no adhesion of sea creatures such as fujibo and sea lettuce for 36 months.
It had good antifouling performance.

On the other hand, with respect to Comparative Paint A of Comparative Example 1, adhesion of living organisms was observed after one month, and the entire coating film had eluted into seawater after six months.

Furthermore, with respect to Comparative Paint B of Comparative Example 2, adhesion of marine organisms was observed after 18 months, and adhesion of marine organisms was observed on the entire surface after 27 months.

Comparative Paint C of Comparative Example 3 also had adhesion after 6 months, and marine organisms were adhering to the entire surface after 12 months.

As described above, since the hydrolyzable resin composition having an antifouling agent in the side chain obtained by the present invention gradually releases the antifouling agent through hydrolysis, it is necessary to add a known antifouling agent. This is an epoch-making resin composition that can maintain its antifouling performance for a long period of time. In addition, antifouling paints containing known antifouling agents, pigments, and additives, if desired, not only improve the antifouling performance, but also eliminate unevenness on the surface of the coating because the coating film gradually dissolves into seawater. In addition to reducing fuel consumption, it also maintains its antifouling performance for an unprecedentedly long period of time.

Claims (3)

[Claims] (1) The end of at least one side chain has a formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (In the formula, X is ▲A mathematical formula, a chemical formula, a table, etc.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼; M is a metal atom with a valence of 2 or more (excluding zinc, copper, tellurium); x is an integer from 1 to 2 ; m is an integer of 1 or more, n is 0 or an integer of 1 or more (however, m+n+1 is equal to the valence of metal M); R_1 is a hydrocarbon having 1 to 10 carbon atoms; R_2 is ▲ mathematical formula, chemical formula, table, etc. There is ▼, ▲ formula,
There are chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -S-, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. A polishing-type antifouling paint composition comprising, as a vehicle, a metal-containing resin composition comprising a resin having at least one group represented by the following. (2) Periodic Table IIa, where M excludes zinc, copper, and tellurium,
A composition according to claim 1 selected from group IIb, IIIa, IVa, VIa, VIb, VIIb and VIII metals. (3) M is Ba, Cd, Hg, Al, Sn, Pb, Si
, Se, Cr, Mo, W, Mn, Fe, Co and Ni
The composition according to claim 2, which is selected from the group consisting of: